Phenylthiovinyl phosphorothioates as insecticides and acaricides

ABSTRACT

The insecticidal and acaricidal compounds have the formula:   AND INCLUDE THE TRANS AND CIS ISOMERIC FORMS OF THE ABOVE COMPOUND AS WELL AS MIXTURES OF THE TRANS AND CIS ISOMERS WHEREIN: R1, R2,8R3 are each lower alkyl, X is chloro, fluoro, or nitro, M IS 0 OR 1, EXCEPT THAT WHEN X is chloro, m is 1 to 3. The compounds are prepared by reaction of an Alpha phenylthioketone with a phosphorothioate compound in the presence of an inert reaction solvent and certain strong bases.

United States Patent Addor et al.

[4 1 Oct. 24, 1972 [54] PI-IENYLTHIOVINY L PHOSPHOROTHIOATES AS INSECTICIDES AND ACARICIDES [72] Inventors: Roger Williams Addor, Pennington; Thomas Walter Drabb, Jr., Trenton, both of NJ [73] Assignee: American Cyanamid Stamford, Conn.

[22] Filed: May 17, 1971 [21] Appl. No.: 144,406

Related US. Application Data [62] Division of Ser. No. 808,006, March 17, 1969,

Pat. No. 3,632,862.

Company,

FOREIGN PATENTS OR APPLICATIONS 1,497,955 10/ 1967 France ..260/949 Primary Examiner-Albert T. Meyers Assistant Examiner-Doris .l. Funderburk Attorney-Robert P. Raymond [57] ABSTRACT The insecticidal and acaricidal compounds have the formula:

" R10 s (x)m and include the trans and cis isomeric forms of the above compound as well as mixtures of the trans and cis isomers'wherein:

R R ,8R are each lower alkyl, X is chloro, fluoro, or nitro, m is 0 or 1, except that when X is chloro, m is 1 to The compounds are prepared by reaction of an aphenylthioketone with a phosphorothioate compound in the presence of an inert reaction solvent and certain strong bases.

10 Claims, No Drawings PHENYLTHIOVINYL'PHOSPHOROTHIOATES AS INSECTICIDES AND ACARICIDFS This application is a divisional of application Ser. No.

808,006, filed Mar. 17, 1969 now U.S. Pat. No.

SUMMARY OF THE INVENTION This invention relates to phenylthiovinyl phosphorothioate compounds of the formulae 1 wherein:

R R and R are each lower alkyl,

X is chloro, fluoro, or nitro, and

m is 0 or 1, except that where X is chloro, m is '1 to 3.

The compounds represented by formula (I) may exist in either a trans or a cis isomeric form as shown by the formulas presented below:

(trans form) H R10 IS literal. n

and

BACKGROUND OF THE INVENTION South African patent 66/5096 disclosesphosphates oftheformulaz H,

R10 0 Ra (X)m E n- Q V Bro H wherein R R and R are as defined above, and wherein X is halogen (chloro or bromo) or lower alkyl and m is 0 to 3. Such phosphates (P=O) are similar to the phosphorothioates (P.=S) of this invention in cases where X maybe chloro (chlorophenyl) or m may be zero (phenyl). However, the phosphorothioates of this invention wherein X is chloro or m is zero exhibit unusual insecticidal activity against certain insect species which is not shown by the related phosphates of the above reference. More particularly, the phenyl and chlorophenyl phosphorothioates of this invention show unusually high potency towards mosquito larvae and datapresented hereinbelow. There is no known relevant'prior art in regard to the phosphorothioates of this invention where X may befluoro or nitro.

Other references disclosing more remotely related 0 prior art compounds are U.S. Pat. .Nos. 2,864,740,

2,864,741, 2,954,320, 2,954,3'l6and Belgian vPat. .No. 702,716.

DESCRIPTION OF THEPREFERRED I EMBODIMENTS COMPOUNDS The following compounds are illustrative of the compounds of this invention (Substituents referto Formula R, R R 2 or 6 4' 3 or 5 CH CH, CH, F CH; CH CH, F CH CH CH: F CH CH CH NO CH CH CH NO CH CH: CH:, NO CH CH CH Cl CH CH; CH, Cl CH, CH CH Cl CH; CH; CH, Cl Cl CH CH, CH: Cl Cl CH CH CH; Cl Cl CH CH CH C H C H CH C H C,H CH F C ,H,, C H CH F C H, C H CH NO C,H C H CH NO C H C li, CH NO C 11 C H, CH Cl C l-l: C H CH: Cl C H, C H, CH Cl C H, C,H CH Cl Cl (3 H,v C,H,, Ch; Cl Cl ChgH5 C,H,, CH, C! Cl a s z s 5 21 5 QB; F 3 E 3 CH C H CH F CH C H CH N0 CH C H, CH; NO CH C H CH NO CH C H CH Cl CH C H, CH Cl CH C H CH Cl CH C H CH Cl Cl CH: C H CH Cl Cl CH C 14, CH Cl Cl n-C H, n-C H C H F n-C l-l n-C H C H NO n-C I-L, n-C -,H, C H Cl n-C H, n-C H C,H Cl Cl n-C H, n-c H C H, Cl Cl n C H n-C H C H Cl Cl n-C H, n-C H, C H F n-C H, n-C l-l, C l-l, F CH CH n-C H F CH;, CH 3 n-C H NO CH CH H-C3H1 Cl CH CH H Cl Cl Cl C H, C,H H C] Cl Cl CH C H H Cl C1 C1 n-C;,l-l n-C H, CH Cl Cl C] CH CH C H, C1 C1 C1 denoted position on the phenyl ring in accordance with the numbering of Formula (I).

PROCESS The compoundsof this invention are conveniently prepared by reacting an a-phenylthioketone of the formula: 1

o H (X)... Rs- J SQ with a phosphorothioate compound of the formula:

l Y Rzo wherein R R R X and m are as defined above and Y is halo (chloro, bromo, fluoro, iodo) in the presence of an inert organic solvent and a strong base selected from the group consisting of alkali metal hydroxides, alkali metal alkoxides, and tetra(lower)alkylammonium hydroxides.

In general, the trans form of the inventive compounds appears to have greater insecticidal and acaricidal activity than the cis form. It therefore becomes desirable to prepare a product mixture containing as much of the trans form as possible. It has been found that when the reaction is carried out, as described above, in more polar solvents, a reaction mixture enriched in the trans form of the compound results.

Illustrative reaction solvents are dimethylformamide,

dimethylsulfoxide, dimethylacetamide, acetonitrile, and the tetrahydrosulfolanes such as tetrahydrothiophene dioxide. Dimethylforrnamide is a preferred solvent.

Suitable bases are potassium tertiary butoxide, sodium methoxide, sodium propoxide, sodium hydroxide, potassium .hydroxide, and tetramethylammonium hydroxide. Potassium hydroxide and sodium hydroxide are preferred bases. A preferred amount of base is about 0.9 to about 1.1 moles per mole of reactant.

A preferred solvent base system is dimethylformamide and either sodium hydroxide or potassium hydroxide due to the high yields and cleaner reaction products resulting therefrom.

The reaction proceeds at temperatures between C. and 100 C. However, a temperature range of to 40 C. is preferred. The reaction can be run at subatmospheric, atmospheric, or superatmospheric pressure, with atmospheric pressure preferred.

All of the required reactants are either readily available on a commercial basis or can be readily prepared by techniques well known to those skilled in the art. Preferably Y will be chloro in the phosphorothioate reactant due to the commercial availability of these particular compounds;

The process of this invention ordinarily produces a mixture of the trans and cis forms of the inventive compounds as discussed above. Substantially pure, i.e., 90 percent or more, trans or cis compounds can be obtained, however, using well known isomer separation techniques such as, for example, chromatography on selective solid substrates such as magnesium silicate. UTILITY The compounds of this invention are useful for controlling a variety of insects and acarina such as those shown in the examples provided hereinbelow. They may be applied to the foliage of plants as dusts or liquid sprays to protect them from pests which feed thereon;

they may also be incorporated in or applied to the soil in order to protect germinating and growing plants from soil-borne pests which attack the root systems and stems of said plants; or they may be applied to the breeding sites of pests to control both the larvae and adult stages of breeding pest populations. In the latter situations the compounds may be applied in conventional formulations such as dusts, dust concentrates, granular materials, wettable powders, emulsifiable concentrates and the like. They may be employed as an flour, silica, charcoal, activated carbon or other inert powders. As a wettable powder, the compounds of this invention may be applied to easily wettable carrier materials, such as attaclay, with or without the aid of surfactants, or on less readily wettable carriers in combination with suitable surfactants.

Advantageously, the compounds of the invention may also be applied by the most modern techniques of low volume or ultra-low volume application wherein the compound is applied essentially as a technical material or in combination with a minor amount of hydrocarbon solvent such as Panasol An-5, Socal 44-L or Esso HAN (all commercially available).

The compounds of this invention may also be applied in combination with other essentially technical materials, such as malathion, which in addition to having insecticidal properties also "serve as a formulation vehicle.

The following exarnplesare provided to further illustrate the invention.

EXAMPLE 1 To an ice-cooled stirred mixture of 8.0 g. of phenylthio-2-propanone and 5.4 g. of potassium t-butoxide in 160 ml. of dimethyl sulfoxide was added 9.1 g. of 0,0-diethyl phosphorochloridothioate. The reaction was complete within one minute and was poured into water. The product was extracted out with methylene chloride and the methylene chloride mixture was water-washed and dried with sodium sulfate. Concentration in vacuo left 12.0 g. (79 percent) of crude product. The nuclear magnetic resonance spectrum showed that this material was about percent trans isomer and about 25 percent of cis isomer. The isolation of the major trans isomer was effected by chromatography on magnesium silicate (Florisil) eluting with petroleum ether and methylene chloride-petroleum ether mixtures and isolated as an oil, n 1.5497.

The proton magnetic resonance spectrum was consistent with the structure with signals at 2.71- (aromatic), 3.97 (olefin C-H), 5.87 (OCH 7.857- (CH C=), and 8.671- (CH CH v Analysis Calcd. for PS O C H C, 49.06; H, 5.97;

Found: c, 49.30; H, 6.14; P, 9.58; s, 20.39.. 7 r 5 EXAMPLE 2 The cis isomer of the compound of Example 1 was prepared in a manner similar to that shown in Example 1 by continuing to elute the magnesium silicate until substantially pure cis isomer was produced.

EXAMPLE 3 Preparation of 0,0-Dimethyl O-l-Methyl-Z-(phenylthio) vinyl Phosphorothioate Following substantially the same'procedure as in Example l, the above compound was prepared in a crude yield of 88 percent. The isolated 100 percent pure trans 25 isomer analyzed as follows:

Analysis Calcd. for PS O C H C, 45.5; H, 5.2; P,

10.7. Found: C, 46.4; H, 5.2; P, 10.9.

EXAMPLE 4 Preparation of 0,0-Diethyl 0-l-Methyl-2-(4- chlorophenylthio)-vinyl Phosphorothioate To a stirred mixture of 10.0 g. of p-chlorophenyl- 40 thioacetone in 150 ml. of dimethylformarnide was added 3.9 g. of ground potassium hydroxide. This was followed by the addition of 9.4 g. of 0,0-diethyl phosphorochloridothioate over a 15 minute period dur- 6 "6065110 minutes, the mixture was poured into water and extracted with benzene. The benzene layer was water-washed and then concentrated in vacuo to give 15.8 g. (91 percent of theory) of product as an orangebrown oil. Analysis by gas-liquid chromatography 4 showed that the crude product was about 90 percent pure 0,0-diethyl 0-1-methyl-2-(p-chl0rophenyl-thio)vinyl phosphorothioate. The nuclear magnetic resonance 0 ;spectrum showed that the relative amounts of trans and icis isomer were 68 and 32 percent, based on the relative strength of the vinyl hydrogen signals at 4.01- and 4.41- respectively.

Column chromatography of 12 g. of such a mixture 15 on 200 g. of Florisil using petroleum ether-methylene chloride mixtures for elution gave 4.6 g. of 95 percent pure trans isomer. The product was a colorless oil having the following analysis:

Trans-0,0-diethyl 0-1-methyl-2-(p-chlorophen- 'ylthio)- vinyl phosphorothioate, n 1.5590.

Anal. Calcd. for c u clro s C, 44.27; H, 5.10;

Cl, 10.06; P, 8.78;

Found: C, 44.24; H, 5.16; Cl, 10.39; P, 8.93; S,

EXAMPLE 5 1.5 Grams of the cis isomer of the compound of Example 4 were prepared in 95 percent purity by continuing to elute the Florisil column of Example 1. The

Following substantially the same procedure as given .in Example 4 and the isomer separation techniques of Examples 1 and 2, a variety of chlorophenyl derivatives of the inventive compound in substantially pure trans and cis form, as well as mixtures of trans and cis were ing which a cooling bath was used to maintain a reacprepared. These derivatives and certain of their propertion temperature of 20 to 30 C. After stirring anaddi 119994991 9129. 29199110 T b e.

TABLE I.-CHLOROPHENYL DERIVATIVES OF THE COMPOUNDS OF THIS INVENTION Product analysis X C1 Crude Calcd. Found yield, R2 R m 2 1 3 1 4 1 5 1 6 1 percent Isomer form C H P c H P CH3 CH3 100% traus. 40.7 4. 3 0.5 40.6 4.1 9.8 i cm 100% trans 47. 3 5.8 8.1 46.8 6. 0 8.0 02115 100% trans 44.3 5.1 8.8 45.0 5.4 9.2 0 H3 C H3 100% trans. 40.7 4. 3 9. 5 40. 8 4. 4 9. 6 CH; CH; 100% trans 40.7 4. 3 0. 5 40.9 4. 4 9. 7 CQHS CH] 100% trans 40. 3 4. 4 s. 0 40.4 4.2 8.2 CH3 CH3 100% trans. 36.8 3.7 8.6 36.9 3. 7 8.5 CH3 CH1 trans. 36.8 3. 7 3. 6 36. 8 3.8 s. 7 CH3 CH3 trans 36.8 3.7 8.6 37.1 3. 7 8.9 CH1 CH3 100% trans. 36. s 3. 7 8.6 as. 3 3. 7 s. 4 CH1 CH; 100% trans- 36.8 3. 7 8.6 37. 4 3. 7 8.8 CH3 CH3 100% trans 36.8 3.7 8.6 36. 7 3.8 8.9 CH3 CH3 9540097,, 01s..-. 40.7 4.3 9. 5 40.99 4. 44 9. 64 CZH5 CH3 93% 01s 44. 3 5. 1 8. 8 44. 44 5. 08 9. 31 02B; CH3 95-100% 015... 40.3 4. 4 8.0 40.57 4. 41 8. 34 CH3 CH3 3571009,, 018.. 36.8 3. 7 8.6 36.71 3.64 8. 71

0 01s CQHS CH3 g trans-0" 44.3 5.1 8. 8 44. 7 5.3 9. 0

72 trans. CH3 CH3 28% cis 33. 0 3.1 34. 7 3.0

CH3 CH3 3 C1 C1 C1 2 33.6 3.1 34.1 3.1

1 Denotes position on the phenyl ring in accordance with numbering of Formula (I). For the compounds given, positions 2 and 6 are equivalent and positions 3 and 5 are equivalent.

2 Purified by molecar distillation. V V

To a stirred mixture of 15.0 g. of 4-nitrophenylthio- Z-propanone in 200 ml. of dimethylsulfoxide was added 6.3 g. of potassium t-butoxide with cooling. After adding 10.5 g. of 0,0-diethyl phosphorochloridothioate, with cooling of the reaction flask, the mixture had become essentially neutral within two minutes. The mixture was then poured into water and the product extracted with methylene chloride. The isolated product amount to 22.0 g. of a dark red oil. A fraction was collected by chromatography on Florisil comprising pure product in a 60:40 trans to cis isomer ratio.

Anal: Calcd. for C H NO PS C, 43.20; H, 4.98; N,

3.32; P, 8.58; S, 17.76. Found (60% trans; 40% cis): C, 42.36; H, 5.09; N,

EXAMPLE 26 The 100 percent pure cis isomer of the product of Example 23 was prepared by further elution of the Florisil column in Example 23.

Anal: Calcd. for C H NO PS C, 43.20; H, 4.98; N,

3.32; P, 8.58; S, 17.76. Found (100% cis): C, 43.22; H, 5.00; N, 3.88; P,

EXAMPLE 27 Preparation of 0,0-Dimethyl-0- l -Methyl-2-( 4- Nitrophenylthio )-vinyl Phosphorothioate EXAMPLE 28 Preparation of 0,0-Dimethyl 0-l-methyl-2-(4- fluorophenylthio)vinyl Phosphorothioate To a stirred mixture of 25.0 g. of 4-fluorophenylthio- 2-propanone in 200 ml. of dimethylsulfoxide was added 15.1 g. of potassium t-butoxide with cooling. After adding 21.7 g. of 0,0-dimethyl phosphorochloridothioate,

with cooling of the reaction flask, the mixture had become essentially neutral within two minutes. It was poured into water and the product was extracted with methylene chloride. The yield of crude product was fluorop henylthio vinyl phosphorothiate 39.0 g. which showed only minor contamination layer chromatography on silica gel. Chromatography on Florisil gave 10.8 g. of percent trans product in the early fractions collected.

Anal: Calcd.for-C, H FO PS C, 42.84; H, 4.54; P,

10.05; S, 20,82. Found (trans) C, 42.83; H, 4.30; P, 9.43; S, 20.81.

EXAMPLE 29 0.5 Grams of pure cis isomer of the compound of Example 28 was prepared by continuing to elute the Florisil column of Example 28.

Anal: Calcd. for C H FO PS C, 42.84; H, 4.54; P,

10.05; s, 20.82 Found (cis): C, 43.75; H, 4.50; P, 9.39; S, 19.60.

' EXAMPLE 30 I Preparation of 0,0-Diethyl 0-1-methyl-2-(4- To a stirred mixture of 15.0 g. of 4-fluorophenylthio- 2-propanone in ml. of dimethylsulfoxide was added 9.2 g. of potassium t-butoxide with cooling. After adding 15.4 g. of 0,0-diethyl phosphorochloridothioate, with cooling of the reaction flask, the mixture had become essentially neutral within two minutes. It was poured into water and the product was extracted with methylene chloride. After water-washing and drying over magnesium sulfate, the mixture was concentrated under vacuum to give 24.2 g. of product as an orange- EXAMPLE 3] 4.6 Grams of pure cis isomer of the compound of Example 30 were isolated by continuing to elute the :Florisil column in Example 30.

Anal: Calcd. for c n rpo s z c, 46.44; H, 5.35; P,

9.21; s, 19.07. Found (cis): C, 47.20; H, 5.35; P, 9.01; S, 18.90.

COMPARITIVE EXAMPLE 1 Activity of Chlorophenyl Compounds as a Mosquito Larvicide v A variety of the chlorophenyl compounds of this invention and a potent prior art chlorophenyl compound were evaluated for mosquito larvicidal properties in accordance with the following procedures. Common malaria mosquito Anopheles quadrimaculatus Say Larvicide Test Groups of 25 larvae of the common malaria mosquito are transferred with a medicine dropper to a 50ml. beaker containing 25 of water. The test comby thin pound is formulated as an emulsion containing 0.1

gram of test material, 0.2 gram of Alrodyne 315 emulsifier, 10 ml. of acetone and 90 ml. of water. This'1,000 ppm emulsion is diluted l-fold with 65 percent acetone-35 percent water to give 100 ppm. One milliliter of the 100 ppm emulsion is pipetted in a sufficient amount of water to produce the desired concentration (expressed as ppm) upon addition thereto of the larvae in 25 ml. of water. Mortality counts are made after 24 hours at 80 F.

LC-50 values are obtained in the standard'manner by plotting percent mortality as a function of the compound concentrations for a variety of concentrations. The term LC-50 means the concentration expressed in ppm required to kill 50 percent of the mosquito larvae.

Results are shown below in Table 11.

TABLE II Activity Against Mosquito Larvae Mosquito Larvae compound as prepared Mortality at LC-SO in Example No. .01 ppm .001 ppm (ppm) 0 CH PriorArt' o,H,o 2i o( :=oH-s@-oi 0 0 017 4 I00 60 .00120 6 100 90 .0014 monochlorophenyl 8 100 12 0015 (trans) 9 100 20 .0018

10 100 0 l l 100 0 0048 12 100 36 .0013 13 100 0 0036 dichlorophenyl l4 100 76 .001 I (trans) 15 100 60 16 100 30 .00135 17 100 36 .0014 5 100 0 .0066 monochlorophenyl 18 100 80 (cis) 19 100 0 .0048 dichlorophenyl 21 100 0 (cis) monochlorophenyl 22 100 0 (trans and cis) trichlorophenyl 23 100 0 (trans and cis) 24 I00 0 .0056

prepared by the recipe of Example 4 of South African Patent 66/5096 except using a p-chlorophenyl reactant. the sulfur analog ofthe prior art compound As can be seen from the above data, the chlorophenpounds of this invention to be from 2.6 to 15 times more toxic toward mosquito larvae than the prior art compound. The compound of Example 4 is the sulfur 5 larvicides.

analog of the prior art compound; yet it is 14 times more toxic towards mosquito larvae than the prior art compound, serving to clearly indicate the unusually high potency of the inventive compounds as mosquito COMPARATIVE EXAMPLE2 Activity of Chlorophenyl Compounds Against In- 10 sects of the Cotton Complex The compounds'of this invention have been found to possess an unusually high activity against certain pests which ravage cotton and other economic crops. Such pests will be referred to hereafter as the cotton complex of insects, said cotton complex comprising in- 25 understood that lygus, tobacco budworm, and bollworm are a threat to a variety of crops in addition to cotton, and that the unusually high potency shown by the compounds of this invention is directed toward the insects of the cotton complex per se and is substantially independent of the vegetative environment in which the insect happens to be found.

The cotton complex of pests is known to be extremely difficult to destroy by treatment with chemical agents. This difficulty is believed due to the ability of these particular insects to develop a resistance to the various chemicals used against them.

A variety of the chlorophenyl compounds of this invention and a potent prior art chlorophenyl compound were evaluated for activity against the cotton complex in accordance with the following procedures.

A. Tarnished Plant Bug Lygus lineolaris (Palisot de Beauvois) Test compounds are prepared as 1,000 ppm solutions in 10 percent acetone, 0.2 percent Alrodyne 315, and 89.8 percent water. A l0-fold dilution is made with 65 percent acetone and 35 percent water. The primary leaves of Sieva lima bean plants are dipped for 3-5 seconds in the test solutions and placed ,in an exhaust hood to dry. When, dry, each leaf is placed in a 4-inch petri dish with a moist filter paper on the bottom. Ten adult Lygus bugs are aspirated from the stock culture and placed in the petri dish. The dishes are covered and held at 80 F. and percent r.h. After 2 days, mortality counts are made.

B. Boll Weevil Anthonomus grandis Boheman Test compounds are prepared as 1,000 ppm solutions in 10 percent acetone, 0.2 percent Alrodyne 315, and 89.8 percent water. A 10-fold dilution is made with percent acetone and 35 percent water. The first or 60 second true leaf of young cotton plants is dipped for 3-5 seconds in the test solution and placed in an exhaust hood to dry. When dry, each leaf is placed in a 4- inch petri dish with a moist filter paper on the bottom. Ten adult boll weevils are removed from the stock cul- 65 ture and placed in the petri dish. The dishes are covered and held at F. and 60 percent r.h. After 2 days, mortality counts are made.

C Tobacco V Budworm H 55 I Heliothis virescens 11 (Fabricius) Test compounds are prepared as 1,000 ppm solutions in 65 percent acetone and 35 percent water. Cotyledons of young cotton plants are dipped for 35 seconds in the test solution and placed in an exhaust hood to dry. When dry, a leaf is placed in a one-ounce plastic medicine cup containing one dental wick saturated with water and two third instar tobacco budworms. The cup is capped and held at 80 F. and 60 percent r.h. After 2 days, mortality counts are made.

Results are presented below in Table III.

TABLE III Activity Against the Cotton Complex Percent Mortality prepared by the recipe of Example 4 of South African Patent 66/5096 except using a p-chlorophenyl reactant. the sulfur analog ofthe prior art compound.

As can be seen from the data of Table III, the compounds of this invention exhibit very high potency toward all three of the difficulty controlled insect species evaluated compared to the low potency of the prior art compound which has no activity against budworm and, no significant activity against lygus or boll weevil. The inventive compounds, on the other hand, give for the most part substantially complete control of lygus and boll weevil while simultaneously also giving varying control over the budworm. The compound of Example 4 is the sulfur analog of the prior art compound; yet it is 5 times more potent against lygus, 2.5 times more potent against boll weevil, and gives percent control vs. no control of budworm as compared to the prior art compound. Certain of the chlorophenyl derivatives of this invention, i.e., the compounds of Examples 6, 9, l0, l7, and 18 give substantially complete control over all three insect species.

EXAMPLE 32 Insecticidal and Acaricidal Activity of the F'henyl,

12 Nitrophenyl, and Fluorophenyl Compounds of this Invention g A. Bean aphid Aphisfabae Scopoli.

Compounds are tested as 0.001 percent solutions or suspensions in 65 percent acetone-35 percent water. Two-inch fiber pots, each containing a nasturtium plant 2 inches high and infested with about 150 aphids 2 days earlier, are placed on a turntable (4 rpm) and sprayed for two revolutions with a No. 154 DeVilbiss Atomizer at 20 psi air pressure. The spray tip is held about six inches from the plants and the spray is directed so as to give complete coverage of the aphids and the plants. The sprayed plants are laid on their sides on white enamel trays. Mortality estimates are made after holding for 2 days at F. and 50 percent r.h.

B. Southern armyworm Prodenia eridania (Crarner) The solutions from the aphid test are diluted to a 01% solution and used for this one. Sieva lima bean primary leaves are dipped for three seconds in the test solution and set in a hood on a screen to dry. When dry, each leaf is placed in a 4-inchpetri dish which has a moist filter paper in the bottom and 10 third-instar armywormlarvae about three-eighths inch long. The dishes are covered and held at F and 60 percent r.h. After 2 days, mortality counts and estimates of the amount of feeding are made. Compounds showing partial kill and/or inhibition of feeding are held an extra day for further observations.

C. Two-spotted spider mite Tetranychus urticae (Koch) Sieva lima bean plants with primary leaves three to four inches long are infested with about adult mites per leaf four hours before use in this test. The mite and egg infested plants are dipped for three seconds in the same solutions used in the aphid test, and the plants set in the hood to dry. They are held for two days at 80 F. 60 percent r.h., and the adult mite mortality estimated on one leaf under a stereoscopic microscope. The other leaf is left on the plant an additional 5 days and then examined at 10X power to estimate the kill of eggs and of newly-hatched nymphs, giving a measure of ovicidal and residual action, respectively.

D. Confused flour beetle Tribolium confusum Jacquelin duVal Compounds are formulated as 1 percent dusts by mixing 0.1 gram of the compound with 9.9 grams of Pyrax ABB talc, wetting with 5 ml. of acetone and grinding with a mortar and pestle until dry. mg. of this 1 percent dust is then blown into the top of a dust settling tower with a short blast of air at 20 psi. The dust is allowed to settle on 4-inch petri dishes for 2 minutes, giving a deposit of approximately 87 mg./sq. foot (0.094 mg./sq. cm) of the 1 percent dust. The dishes are removed and 25 adult confused flour beetles are added immediately. The dishes are held for three days at 80 F. and 60 percent r.h., following which mortality counts are made.

E. Large mildweed bug Oncopeltus fasciatus Dallas The 1 percent dusts described above are used in this test. 25 mg. of the 1 percent dust is sprinkled evenly over the glass bottom of a 7-inch diameter cage, using a screen-bottom plastic cup about Xi-inch diameter as an applicator, giving a deposit of approximately 94 mg./sq. ft. 0.108 m g./sq. cm.) of the l percent dust. Water is supplied in a 2-ounce bottle with a cotton wick, twenty adult bugs are added and a screen cover placed on the top. Mortality counts are made after holding for 3 days at 80 F. and 60 percent r.h.

F. German cockroach Blattella germanica Linnaeus) The procedure is the same as for the large milkweed bug test, except that in this test only adult males are used.

The test is the same as with the rootworms except that 10-day old wireworm larvae are used.

K. Tamished plant bug Lygus lineolaris (Palisot deBeauvois) L. Boll weevil Anthonomus grandis Boheman M. Tobacco budworm Heliothis virescens (Fabricius) The test for insect species K, L, and M are the same as given in Comparative Example 2.

G. Common malaria mosquito Anopheles Bes hs ares; own kejlowinlllable IV.

TABLE IV.-INSECTICIDAL AND ACARICIDAL ACTIVITY OF THE PHENYL, NITROPHENYL, AND FLUOROPHENYL COMPOUNDS OF THIS INVENTION (EXPRES SED AS PERCENT MORTALITY) Mosquito Boll Bud- Compounds us Aphids. SAW, Mites, Larvae, Adults, Fly, RW. W.W. Lygus, weevil, worm, prepared in 100 10 TC M13 GC Cl 10 50 10 lb./ 10 lb 100 100 1,000 Examph: No. p.p.m. p.p.m. p.p.m. 1% 1% 1% p.p.m. p.p.m. p.p.m. acre acre p.p.m. p.p.m. p.p.m.

I SAW Southern Armyworm. Z T C= Trz'bolium confusum (confused flour beetle). 3 MB =Milkweed Bug. 4 G0 German cockroach. 5 R.W.= Rootworm. 6 W.W.= Wirewom1. g H quadrimaculatus Say The data of Table IV indicate that the compounds 1. Larvicide test This is the same test given in Comparative Example l. 2. Adulticide test. v

Test compounds are prepared as 10 ppm solutions in acetone. Glass microscope slides are dipped in the test solutions and allowed to dry in a horizontal position. When dry, they are individually placed in 4-ounce wide mouth bottles and 10 4 to 5 day old mosquitoes of mixed sexes are added to each bottle. A piece of cotton gauze serves as a lid, and a wad of cotton soaked in 10 percent sugar solution serves as food. Mortality counts are made after 24 hours of continuous exposure to the residue on the glass slide; temperature is 80 F. and r.h. is 60 percent. H. Housefly Musca domestica Linnaeus Groups of 25 adult female houseflies are lightly anesthetized with CO placed in wide-mouth pint mason jars, and covered with a screen cap. The test compound is formulated as an emulsion containing 0.1 gram of test material, 0.2 gram of Alrodyne 315 emulsifier, 10 m1. of acetone and 90 ml. of water. Two milliliters of this emulsion are diluted to ml. with 10 percent sugar solution in a 10-gram glass vial, giving a concentration of 50 ppm. The mouth of the vial is covered with a single layer of cheesecloth, inverted and placed on the screen cap, so that the flies can feed on the solution through the screen. Mortality counts are made after 2 days at 80 F.

1. Southern corn rootworm Diabrotica undecimpunctata howardi Barber The compound is formulated as a dust and incorporated into the soil at the equivalent of 10 pounds per 6-inch acre. The soil is sub-sampled into l-ounce wide mouth bottles, and 10 6 to 8 day old rootworm larvae added to each bottle, which is then capped. Mortality counts are made after 6 days at 80 F., 60 percent r.h.

J. False wireworm Eleodes suturalis (Say) are very active against mosquito larvae; certain com-- pounds, particularly the fluorophenyl compounds, exhibit high potency against insects of the cotton complex.

The chlorophenyl compounds of this invention such as those illustrated in Table l hereinabove exhibit activity against insects and acarina such as aphids, southern armyworms, mites, confused flour beetles, milkweed bugs, German cockroaches, adult mosquitoes, flies, rootworms, and wireworms, which is similar to that shown in Table IV.

We claim:

1. A method for controlling insects selected from the group consisting of mosquito larvae, lygus, boil weevil, bollworm and tobacco budworm, which comprises contacting said insects with an insecticidally effective amountof atleast one compound of theformula:

which includes the trans form, the cis form or mixtures of the trans and cis form of said compound, wherein:

R R and R are each lower alkyl, X is chloro, and m is 1 to 3. 2. A method according to claim 1 wherein the compound has the formula:

pound has the formula:

3. A method according claim 1 wherein the compound has the formula:

CzHnO 4. method according to claim 1 wherein the com- Cl CH O 3 -5. A method for controlling insects and acarina which comprises applying to said insects and acarina an insecticidally and acaricidally effective amount of at least one compound of the formula:

R which includes the trans form, the cis form or mixtures of the trans and cis form of said compound, wherein:

R R and R are each lower alkyl,

X is selected from the group consisting of fluoro and nitro, and

m is O or 1.

6. A method according 5 wherein the compound has the formula:

7. A method for controlling soil borne insects which comprises applying to soil containing said insects an insecticidally effective amount of a compound according to claim 5.

8. A method according to claim 7 wherein the compound has the formula:

CzHgO 

2. A method according to claim 1 wherein the compound has the formula:
 3. A method according to claim 1 wherein the compound has the formula:
 5. A method for controlling insects and acarina which comprises applying to said insects and acarina an insecticidally and acaricidally effective amount of at least one compound of the formula:
 6. A method according to claim 5 wherein the compound has the formula:
 7. A method for controlling soil borne insects which comprises applying to soil containing said insects an insecticidally effective amount of a compound according to claim
 5. 8. A method according to claim 7 wherein the compound has the formula:
 9. A method for protecting vegetation from destruction by insects and acarina which comprises applying to said vegetation an insecticidally and acaricidally effective amount of a compound according to claim
 5. 10. A method according to claim 9 wherein the compound has the formula: 